INTRODUCTION

The liquid crystal state is a distinct phase of matter observed between the crystalline solid
and isotropic liquid states. Liquid crystal is a state of matter whose properties are between
those of conventional liquids and those of liquid crystals. Liquid crystal phases represent a
unique state of matter characterized by both mobility and order on a molecular and at the
supramolecular levels. This behavior appears under given conditions, when phases with a
characteristic order intermediate to that of a three dimensional ordered solid and a
completely disorder liquid are formed. As the name suggests, liquid crystals are materials
which share some structural properties that are found in solid crystals (e.g., diamond), while
at the same time displaying flow behavior observed in classic liquids (e.g., water). They can
therefore be thought of as an intermediate state of matter, existing between the solid and
liquid phase. In liquid crystal materials, the molecules lose the positional ordering found in
solids, but not their orientation ordering (i.e., how the molecules are aligned in a sample).
The orientation ordering and fluid flow in liquid crystal materials are coupled to each other,
where molecular rotation can cause flow and vice versa. In classic liquids, the molecules
have no positional or orientation ordering. Molecules in the crystalline state possess
orientation and 3 dimensional positional orders. That is the constituent molecules of highly
structure solid occupy specific sites in 3 dimensional lattice and point their axis in fixed
direction. Liquid crystals, as their name implies, are substances that exhibit properties of
both liquids and crystals. Specifically, their molecules have the high orientation order found
in crystalline solids as well as the low positional order found in liquids or amorphous glasses.
Most liquid crystals are thermotropic; their degree of orientation and positional order
depends on temperature and so their liquid crystalline phase occurs within a limited
temperature range between the solid and liquid phase.
Liquid crystal molecules are typically ‘rod shaped’ – long and thin with a rigid center that
allows them to maintain their shape. They also have flexible ends, which means that they
can still flow past each other with ease. Molecules with this shape are known as calamitic
liquid crystals. It is also possible to find liquid crystals made up of disc-shaped molecules;
these are given the name discotic liquid crystals. The same rules apply here – a rigid center
is essential in order for the molecule to keep its shape and flexible edges allow ease of
movement. Furthermore, polymeric liquid crystals as well as those whose behavior depend
on their concentration in solution (lyotropic liquid crystals) have also been discovered.

Historical Background
In 1888, the Austrian chemist Friedrich Reinitzer, working in the Institute of Plant Physiology
at the University of Prague, discovered a strange phenomenon. Reinitzer was conducting
experiments on a cholesterol based substance trying to figure out the correct formula and
molecular weight of cholesterol. When he tried to precisely determine the melting point,
which is an important indicator of the purity of a substance, he was struck by the fact that
this substance seemed to have two melting points. At 145.5°C the solid crystal melted into a
cloudy liquid which existed until 178.5°C where the cloudiness suddenly disappeared, giving
way to a clear transparent liquid. At first Reinitzer thought that this might be a sign of
impurities in the material, but further purification did not bring any changes to this
behavior. Puzzled by his discovery, Reinitzer turned for help to the German physicist Otto
Lehmann, who was an expert in crystal optics. Lehmann became convinced that the cloudy
liquid had a unique kind of order. In contrast, the transparent liquid at higher temperature
had the characteristic disordered state of all common liquids. Eventually he realized that the
cloudy liquid was a new state of matter and coined the name "liquid crystal," illustrating
that it was something between a liquid and a solid, sharing important properties of both. In
a normal liquid the properties are isotropic, i.e. the same in all directions. In a liquid crystal
they are not; they strongly depend on direction even if the substance itself is fluid. This new
idea was challenged by the scientific community, and some scientists claimed that the
newly-discovered state probably was just a mixture of solid and liquid components. But
between 1910 and 1930 conclusive experiments and early theories supported the liquid
crystal concept at the same time that new types of liquid crystalline states of order were
discovered.

At the early time of Reinitzer and Lehmann, scientists only knew three states of matter. The
general idea was that all matter normally had one melting point, where it turns from solid to
liquid, and a boiling point where it turns from liquid to gas. Water is a good example of this
view. It melts at 0°C and it boils and becomes steam, which is water in its gaseous form, at
100°C. Today, thanks to Reinitzer, Lehmann and their followers, we know that literally
thousands of substances have a diversity of other states. Some of them have been found
very usable in several technical innovations, among which liquid crystal screens and liquid
crystal thermometers may be the best known. In the 1960s, a French theoretical physicist,
Pierre-Gilles de Gennes, who had been working with magnetism and superconductivity,
turned his interest to liquid crystals and soon found fascinating analogies between liquid
crystals and superconductors as well as magnetic materials. His work was rewarded with the
Nobel Prize in Physics 1991. The modern development of liquid crystal science has since
been deeply influenced by the work of Pierre-Gilles de Gennes.

What is So Special about Liquid Crystals?

Liquid crystals are partly ordered materials, somewhere between their solid and liquid
phases. Their molecules are often shaped like rods or plates or some other forms that
encourage them to align collectively along a certain direction. The order of liquid crystals
can be manipulated with mechanical, magnetic or electric forces. Finally, liquid crystals are
temperature sensitive since they turn into solid if it is too cold, and into liquid if it is too hot.
This phenomenon can, for instance, be observed on laptop screens when it is very hot or
very cold.

There are various ways of classifying LCs based on the molar mass of the constituent
molecules, that is, low molar mass (monomeric and oligomeric) and high molar mass
(polymeric) LCs; based on how the liquid crystalline phase has been obtained, that is, by
adding solvent (lyotropic) or by varying the temperature (thermotropic); based on the
nature of the constituent molecules (organic, inorganic, and organometallic); based on the
geometrical shape of the molecules (rod-like, disk-like, banana-like); and based on the
organization of the molecules in the liquid crystalline phase (nematic, smectic, columnar,
helical, B phases, etc.). The classification of LCs is shown in figure (1.3). However, the most
widely recognized and used classification of LCs is into two major categories: (a)
thermotropic LCs (mesophase formation is temperature dependent) and (b) lyotropic LCs
(mesophase formation is solvent and concentration dependent). If a compound displays
both thermotropic and lyotropic liquid crystalline phases, then it is called amphotropic LC (8).

Figure1.3 Classification of LCs. (8)

1.3 Lyotropic Liquid Crystals:

Lyotropic LCs also known as anisotropic solutions, are formed by dissolving amphiphilic
compounds in suitable solvents under appropriate conditions of concentration and
temperature. The amphiphilic compounds are characterized by two distinct parts of
contrasting character: a hydrophilic polar head and a hydrophobic nonpolar tail. Apart from
temperature, both the concentration of the solute and the solvent (most often water) also
play a very significant role in lyotropic LC systems. Typical examples of lyotropic LCs are
soaps in water and various phospholipids. Lyotropic LC phases can have positional order in
one (lamellar) two (columnar hexagonal), or three (cubic) dimensions. When a small amount
of amphiphilic material is dissolved in a polar solvent such as water, it goes into the solution.
As the concentration of the material is increased, the hydrophobic tails assemble together
and present the hydrophilic polar heads to the solvent, thereby arranging themselves into
spheres called micelles figure (1.4). So the polar head groups are on the surface of the
micelle and the nonpolar hydrocarbon chains are toward the center. The micelles are stable
as long as the amount of amphiphilic material is above a certain concentration called critical
micelle concentration (CMC). (8)

Figure1.4 Cross sections of micelles and reverse micelles formed by surfactant molecules and
lyotropic liquid crystalline phases: (a) lamellar, (b) bicontineous cubic, (c)hexagonal
columnar, and (d) miceller cubic. (8)

1.4 Thermotropic Liquid Crystals:

When the liquid crystalline phases are obtained by varying the temperature of the
compounds, they are called thermotropic LCs. If the temperature increases, thermal motion
will destroy the order of the LC phase, pushing the material into a conventional isotropic
liquid phase. At too low temperature, most LC materials will form a conventional crystal. (4)
(9)
Thermotropic divided into three main classes according to the shape and structure of the
molecules , the three classes are rod like (calamitic), disk like (discotic) and banana like LCs.
(8)
Figure (1.5) show the classes of thermotropic LCs.
( a) (b)

(c)

Figure 1.5 Molecular structure of the three classes of thermotropic LCs (a) rod like [5CB], (b)
disc like (benzene-hexa-n-alkanoate derivatives), and (c) banana-shaped liquid crystals.(10)
1.4.1 Calamitic Liquid Crystals (rod like):
The most common type of molecules that form thermotropic mesophase are rod-like
molecules. These molecules possess an elongated shape, that is, the molecular length (l) is
significantly greater than the molecular breadth (b), as depicted in figure (1.6).

Figure 1.6 Representation of a calamitic LC molecule where l>>b. (8)

The geometric shape anisotropy in combination with interaction anisotropy and
microsegregation of incompatible parts in calamitic LCs leads to a number of mesophase
morphologies. Most of the calamitic liquid crystalline compounds consist of two or more
ring structures, bonded together directly or via linking groups. They usually have terminal
hydrocarbon chains and sometimes lateral substituents as well. The typical chemical
structure of these molecules can be represented by the general template, as shown in figure
(1.7), where A and B are core units (benzene, naphthalene, biphenyl, etc.), R and R' are
flexible moieties such as normal and/or branched alkyl groups, M and N are generally
small lateral substituents ( ̶ Cl, ̶ Br, ̶ NO 2, ̶ CH3, ̶ OCH3, ̶ CN, etc.). Y is a linking group to the
core units and X and Z are linking groups of terminal chains and core units like (S, N, O, NH,
CO, etc.). The nature of the central core, linking groups, and lateral substituents impart
significant effect on the mesophase morphology and physical properties of calamitic LCs.

Calamitic LCs generally exhibit two types of mesophases: (a) nematic and (b) smectic.

Figure 1.7 General template for calamitic LC molecules.(8)

[Link] Nematic phases:

One of the most common LC phases is the nematic. The word nematic comes from the
Greek word nema which means "thread". In a nematic phase, the calamitic or rodshaped
organic molecules have no positional order, but they self-align to have longrange
orientational order with their long axes roughly parallel. (11) Thus, the molecules are free to
flow and their center of mass positions are randomly distributed as in a liquid, but still
maintain their long-range directional order. Most nematics are uniaxial: they have one axis
that is longer and preferred, with the other two being equivalent (can be approximated as
cylinders or rods). However, some liquid crystals are biaxial nematics, meaning that in
addition to orienting their long axis, they also orient along a secondary axis. (12) Nematics
have fluidity similar to that of ordinary (isotropic) liquids but they can be easily aligned by an
external magnetic or electric field. Aligned nematics have the optical properties of uniaxial
crystals and this makes them extremely useful in liquid crystal displays (LCD).(13)

(a) (b)
Figure 1.8 (a) Alignment in a nematic phase (b) Phase transition between a nematic (left)
and smectic A (right) phases observed between crossed polarizers. The black color
corresponds to isotropic medium. (12)

[Link] Smectic phases:

The smectic phases at low temperatures form characteristic layers that can slip over one
another in a manner similar to that of soap. The word "smectic" originates from the Latin
word "smecticus", means cleaning, or having soap like properties. The smectics are thus
positionally ordered along one direction. In the Smectic A phase, the molecules are oriented
along the layer normal, while in the Smectic C phase they are tilted away from the layer
normal. These phases are liquid-like within the layers. There are many different smectic
phases, all characterized by different types and degrees of positional and orientational
order. (4)(14)

Figure 1.9 Schematic of alignment in the smectic phases. The smectic A phase (left) has
molecules organized into layers. In the smectic C phase (right), the molecules are tilted inside
the layers.(12)

1.4.2 Discotic Liquid Crystals (disk like):

In September 1977,(15) Chandrasekhar and colleagues at Raman Research Institute, India

reported the first observation of thermotropic mesomorphism in pure, single component
systems of relatively simple plate like, or more appropriately disk-like molecules. They
designed and synthesized a number of benzene hexa-n-alkanoates and investigated possible
mesomorphism in this novel molecular architecture. By thermodynamic, optical, and x-ray
studies, they could establish that these materials form a new class of LCs in which molecules
are stacked one on top of the other in columns, and the columns in turn constituted a 2D
hexagonal arrangement. Selforganization of disk-like molecules forms an entirely new class
of LC, quite different from the classical LCs formed by rod-like molecules that had been
known since they were observed by Friedrich Reinitzer in 1888. (5) The disk-like molecules
spontaneously self-assemble into 1D stacks, which in turn self-organize on various 2D
lattices; the third dimension has no translational order figure (1.10). (8)
Figure 1.10 Self-assembly and self-organization of discotic liquid crystalline molecules into
columnar
phases.(8)

[Link] Types of Discotic Liquid Crystal Mesophase:

There are two types of discotic liquid crystal mesophase. First, the Nematic phase or the least
ordered mesophase (usually occur at highest temperature). Disk-like molecules in such a phase
have orientational order but no positional order. Only few examples of discogens have this
mesophase.

The other mesophase is Columnar phase in which the molecules are stacked into columns, the
columns then being organized in a two-dimensional lattice. Molecules in such a phase have a
positional order in two dimensions and are disordered in the third. Columnar phases are very
rich and are normally classified at three levels; according to the symmetry of the two-
dimensional array, the orientation of the core with respect to the column axis, and finally the
degree of order within the column. The columnar phase divided into hexagonal and rectangular
columnar phases as shown in figure

(1.11). (16)
11

Figure 1.11 The phases formed by disc-like molecules are characterized by the degree of
positional order and symmetry.(16)

[Link] Structure of the Discotic Mesogens:

Molecules forming DLCs are typically made of a central discotic core substituted by 3-12
saturated chains of three or more carbon atoms phthalocyanines and triphenylenes are the
typical examples of discotic molecules figure (1.12).

Figure 1.12 Typical examples of discotic molecules.

These materials often have two-, three-, four-, or six-fold rotational symmetry. However, there
are many exceptions, and materials with low symmetry, a nonplanar, nonaromatic core having
shorter number of chains are also documented. The liquid crystallinity results from the
microsegregation of the two constituents: the crystalline character is promoted by the
interaction between the conjugated cores while the liquid character originates from the melting
of the saturated alkyl chains in the mesophase. Such discotic molecules organize spontaneously
in the form of 1D columns, which can be oriented easily and possess self-healing properties,
that is, the capacity of repairing structural defects in contrast to crystalline materials. The
search for such mesophases is mostly ruled by subtle changes in the number, size, and nature
of the lateral chains in addition to the central core. A general template for discotic mesogens is
shown in figure (1.13). By tailoring the shape, size, and nature of the central core as well as the
type of the attached side chains, compounds with different abilities to self-organize into
different mesophase morphologies can be obtained.(8)

Figure 1.13 General template for DLC molecular architecture . X is a linking group like
(NH,COO,S,O, etc.),Y is a lateral group like (Cl, Br, CH3, OCH3, CN, NO2, etc.).(8)

1.4.3 Bent-Core Liquid Crystals (Banana like):

Vorlander (17), a pioneer in the field of LC synthesis, has synthesized several bent-core LCs and
reported the mesogenic properties in 1929, mentioning that the thermal stability of the
mesophase is low compared to straight core analogues. Matsunaga (18) and coworkers also
synthesized bent-core mesogens in the early 1990s but did not realize the physical importance
of the molecules before the discovery of polar switching in these compounds in 1996. Bent-
shaped molecules provide access to mesophase with polar order and supramolecular chirality
despite the mesogens being achiral. Typically, their molecular structure can be regarded as
being composed of three units: an angular central core, two linear rigid cores, and terminal
chains figure (1.14). (8)
 Figure 1.14 General template for banana LC molecules, X, Y are linking groups like (NH, S, O,
COO, etc.), Z lateral substituents like (NO2, OCH3, CH3, OH, Cl, Br, CN,etc.).

1.5 Application of Liquid Crystals:

Liquid crystals have a large number of applications due to their electro-optical, magneto-
optical, electro-chromic and thermo-chromic properties, which are important in industrial and
medical applications. These applications include display-device technology, medical
applications, gas-liquid chromatography, and cosmetics applications.

The major use of liquid crystal displays is currently in watches and small portable calculators
…. etc. Liquid crystal displays visibility in high ambient light, easily changed pattering and size,
variation in color, operation in transmissive or reflective mode and more. (19)

Liquid crystals have gained a great interest as stationary phase in gas liquid chromatography
(G.L.C.). They are used in the separation of close boiling compounds on the bases of their
molecular shape. One of the most interesting separations that have been achieved on liquid
crystals is in separation of optical isomers. Certain liquid crystal stationary phases
are suitable for programmed-temperatures gas
chromatography and for work at temperature of about 300oC. (20)
The medical applications of liquid crystals such as cholesteric nematic type, include disposable
oral thermometry, neurology, oncology, pediatrics surgery, and podiatry. To be more specific
these medical applications include detection of breast cancer, location of the placenta, blood
flow patterns in extremities of the human anatomy and observation of skin temperature change
following blockage of the sympathetic nervous system. Liquid crystals used in many skin care
products. The first and probably most successful product is Eyzon, which incorporates very
attractive coils of iridescent liquid crystal in a clear gel. It is probable that vitamin A palmitateis
mixed with the liquid crystal. (21)

Since 1977 when Chandrasekhar et al. first discovered discotic liquid crystals (DLCs) (4), DLCs
have become an important member of liquid crystals. DLCs can easily self-assembly to be highly
ordered columnar mesophases, which allow the electrons or holes to migrate along the
columnar structures. These properties, as a result, have made DLCs an excellent candidate for
photo-electronic semiconductor materials (22).

The synthesis route of a discotic liquid crystal was investigated, because these molecules have
potentially important industrial applications due to unique properties. Discotic liquid crystals
are well ordered types of liquid crystal that make their liquid crystal state easy to control. In
addition, they can be easily polymerized and they have conducting properties. All these
properties make discotic liquid crystals of particular interests especially if they are intended for
electronic devices. (23)

1.6 Literature Survey:

(24)
In 1984, S. Takenaka, et. al synthesized a triester derivative of benzene which exhibit a
discotic nematic phase.

Figure 1.15 Triester derivative of benzene.

In 2001, B. G. Kim and coworkers synthesized compounds containing oxadiazole side arms
figure (1.16) exhibit discotic nematic phase behavior. (25)
Figure 1.16 Oxadiazole side arms discotic compounds.

In 2001, J. H. Lee and coworkers synthesized a various hydrogen bonded supramolecular

discotic compounds, which exhibit the ND phase (26) figure (1.17).
 Figure 1.17 Various hydrogenbonded supramolecular discotic compounds. In 2004, H.
Meier and coworkers synthesized a stilbinoid side arms discotic compounds figure (1.18) which
exhibit discotic nematic phase behavior. (27)

Figure 1.18 Stilbinoid side arms discotic compounds.

In 2005, A. Grafe, et. al (28) synthesized a discotic liquid crystalline trimers (a-d) figure (1.19)
containing benzene as the central core show only the columnar nematic phase in the pure
compounds.

Figure 1.19 Discotic liquid crystalline trimers containing benzene as the central core.

In 2006, M. J. Jeong and coworkers synthesized a hydrazone -based side-arms discotic

compounds figure (1.20) which exhibit discotic nematic phase behavior. (29)
Figure 1.20 Hydrazone based side arms discotic compounds.
In 2011, S. Kumar and S. K. Gupta (30) synthesized a novel discotic core by fusing imidazole unit
with well-known triphenylene discotic core as in figure (1.21). Two (new imidazole fused
unsymmetrically substituted triphenylene) derivatives were prepared and characterized. These
triphenylenoimidazole derivatives were found to exhibit hexagonal columnar mesomorphism
over a wide temperature range.

Figure 1.21 New imidazole fused unsymmetrically substituted triphenylene derivatives.

In 2014, G. Y. Yeap and coworkers synthesized a symmetrical trimeric star-shaped mesogens

based on 1,3,5-trisubstituted benzene incorporating Schiff base and azobenzene fragments as
the peripheral units figure (1.22). PSB-Cl-5 show during the cooling cycle from the isotropic, (a)
Schlieren texture two- and four-fold brushes of N phase appeared followed by the (b) SmC
phase. PSB-Br-5 exhibiting the focal conic fan-shaped texture of SmA phase. PAZ-Cl-4 show (a)
Schlieren texture of N phase upon cooling and followed by the (b) fan-shaped texture
characteristic of SmA phase. PAZ-Br-5 upon cooling showing the appearance of transition bars
across the fanshaped during the SmA to SmB phase transition.(31)

Figure 1.22 Three-armed star-shaped mesogens PSB-X-n and PAZ-X-n.